JPH05224330A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material high in sensitivity in a red wavelength region and small in residual color stains after development processing and occurrence of black spots even during storage at high temperature by spectrally sensitizing the photosensitive material by a specified spectral sensitizing dye and incorporating a hydrazine derivative in a silver halide emulsion layer and/or its adjacent layer. CONSTITUTION:The photosensitive material is spectrally sensitized by at least one kind of the spectral sensitizing dye selected from formula I to have the photosensitive wavelength region substantially in 600-700nm, and the silver halide emulsion layer and/or its adjacent layer contains the hydrazine derivative. In formula I, Z is an atomic group necessary to form a thiazole, benzo- or naphtho-thiazole, selenazole, benzo- or naphtho-selenazole; and each of R1-R5 is, independently, H, optionally substituted alkyl, or aryl, and at least 2 of them are each an organic group having a water-soluble group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more particularly to a photographic light-sensitive material capable of obtaining high contrast.

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous-tone originals into halftone images. In this step, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of 0.2 μm, a narrow particle distribution and a well-formed particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion. By processing this lith-type silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, it is a method using a hydrazine derivative as described in JP-A-56-106244. According to these methods, it is possible to obtain a high contrast image by processing with a developing solution which has good preservative property and is capable of rapid processing.

On the other hand, silver halide photographic light-sensitive materials which emit light in the red wavelength region, for example, which is recorded by a laser light source, have been frequently used in the fields of printing plate making and medical field. Especially in the field of printing and plate making, a large number of facsimiles and color scanner films are used, and as a light source, a HeNe laser having an output wavelength of 632.8 nm and 650-
A light emitting diode (LED) or 6 with an output wavelength of 700 nm
A red semiconductor laser having an output wavelength of 70 to 680 nm is mainly used.

From the viewpoint of low cost and weight saving, these exposure apparatuses are mainly of the plane scanning type or the inner surface scanning type. In the case of exposure by a plane scanning type or an inner surface scanning type, since a fringe easily appears on the film, it is preferable to use a light-sensitive material capable of obtaining a high contrast image. As one of the preferable light-sensitive materials, a method in which the hydrazine derivative as described above and a panchromatic sensitizing dye for spectrally sensitizing at 600 to 700 nm are combined can be used. As a concrete example, JP-A-2-124560,
It is described in the specifications of the same, such as 2-125248 and 3-100543.

In silver halide photographic light-sensitive materials, it is important to improve the residual color contamination after development and to improve the storage stability of the light-sensitive material, in addition to the high spectral sensitization characteristics in the above red light source. It is a technology.

Particularly, as a recent trend, due to the speeding up, simplification or low replenishment of processing, residual color contamination during processing tends to be insufficient. As a result, there is a problem in that the performance is hindered and the commercial value is impaired.

The light-sensitive material using the panchromatic sensitizing dye described in the above specific examples was insufficient in removing residual color stains. In addition, during storage, particularly when stored at high temperature, sand-like defects, so-called black spots, tend to occur in the unexposed portion, which is a problem.

A light-sensitive material containing a sensitizing dye of the general formula [I] of the present invention is described in JP-A-3-171135, but no light-sensitive material utilizing a hydrazine derivative is mentioned and black There is no suggestion as a technique for improving spots, and development of a light-sensitive material spectrally sensitized with a sensitizing dye of the formula [I] in the presence of a hydrazine derivative is disclosed in Swiss Patent 677409. Only an example in which hydrazine is added to a developing solution is described, and a hydrazine derivative is contained in a light-sensitive material spectrally sensitized with a sensitizing dye of the general formula [I] to provide a high contrast and a good black spot. Is not listed.

The improvement of black spots by adding a sensitizing dye having a water-soluble group is disclosed in JP-A-63-108335 and the like, but the panchromatic sensitizing dye described is safe. There was a problem that fog increased due to light.

Further, when a panchromatic sensitizing dye is used, since it has a light-sensitive region in the red region, it emits 450 as safe light.
It is common to use light in the blue-green range of ~ 550 nm. However, the safety light for panchromatic light overlaps the photosensitive wavelength of the photosensitive material and cannot be brightened, which hinders work in a dark room.

[0014]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide light-sensitive material which has high sensitivity in the red wavelength region and has less residual color contamination after development processing.

A second object of the present invention is to provide a silver halide light-sensitive material which causes little black spots even when stored at high temperature.

A third object of the present invention is to provide a silver halide light-sensitive material which is less likely to cause fogging with respect to safe light.

[0017]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and at least one spectral enhancement compound selected from the following general formula [I]. Substantially 600 to 700 nm depending on the dye
It is achieved by a silver halide photographic light-sensitive material, which is spectrally sensitized so as to have a light-sensitive area and which contains a hydrazine derivative in the silver halide emulsion layer and / or its adjacent layer.

At least two of the water-soluble groups are acids and bases which can be ionized in an aqueous solution, and a sensitizing dye having a water-soluble group having a pKa of 4 to 11, and the water-soluble group In a preferred embodiment, at least one of the functional groups is a sensitizing dye having a water-soluble group having a pKa of 4 or less.

[0019]

[Chemical 2]

[In the formula, Z represents an atomic group necessary for completing a thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, or naphthoselenazole ring. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group. However, R ₁ , R ₂ , R ₃ ,
At least two of R ₄ and R ₅ represent a group having an organic group carrying a water-soluble group. The present invention will be described in detail below.

In the above general formula [I], at least two of R _{1 to} R ₅ represent an organic group carrying a water-soluble group. The water-soluble group referred to here is the structure and physiology of the compound. Ha used in the so-called structure-activity relationship that captures the relationship with activity
Indicates that the nsch method has a negative π value. In addition, Hans
Regarding the ch method, J. Med. Chem, 16, 1207 (1973), 20, 304 (1)
979). At least three of R _{1 to} R ₅ are preferably organic groups carrying a water-soluble group.

Of these water-soluble groups, dyes which are ionized in an aqueous solution and have one or more pKa of 4 to 11 are preferable. Particularly preferably, one or more is 4
Organic groups having a pKa of -11 and at least one having a pKa of 4 or less have excellent spectral sensitivity and little residual color contamination. Most preferably, two or more dyes have a pKa of 1 to 4 and one or more dyes have a pKa of 4 or less.

One of the examples of specific functional groups showing a preferable pKa
Examples are shown below, but the present invention is not limited thereto.

PKa of 4 to 11-(CH ₂ ) _n COOM, --C ₆ H ₄ COOM, --CH ₂ C ₆ H ₄ COOM, --CH ₂ --CH
_{= CH-CH 2 COOM, -} (CH 2) 2 SO 2 NHC 6 H 4, -CH 2 CH 2 CONH 2 pKa of 4 or less things _{- (CH 2) n SO 3} M, -C 6 H 4 SO 3 M, -CH ₂ C ₆ H ₄ SO ₃ M, -CH ₂ -CH
_{= CH-CH 2 SO 3 M} -CH 2 CH (SO 3 M) CH 3 in the above formula, n represents 2 to 4, M represents a hydrogen atom, an alkali metal atom or an ammonium group, an organic amine group.

R ₅ is preferably a water-soluble group.

More preferably, R ₅ is a water-soluble group, and R ₁ and R ₂ are both water-soluble groups.

In the general formula [I], the substituents of R _{1 to} R ₅ other than the above are alkyl groups which are linear or branched,
It may be cyclic and is preferably a methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl or octyl group having up to 8 carbon atoms.

Preferred examples of the substituted alkyl group include a halogen atom (for example, chlorine, bromine, fluorine atom, etc.), a hydroxy group, a monocyclic or bicyclic aryl group having 6 to 12 carbon atoms (in this aryl group, For example, a phenyl group may be substituted with an alkyl group having up to 4 carbon atoms, a nitro group, a halogen atom or the like). A nitro group or a halogen atom may be substituted on the benzene ring with an alkoxycarbonyl group having up to 4 carbon atoms (eg, ethoxycarbonyl group) or an acyl group having up to 4 carbon atoms (eg, acetyl group, benzoyl group). ), And an alkoxy group having up to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.).

The aryl group is a phenyl group or naphthyl group which may have a substituent, and examples of the substituent include an alkyl group having up to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.). be able to.

The thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazol and naphthoselenazol ring represented by Z in the above general formula [I] each have a usual substituent used in the spectral sensitizing dye. The substituent may be, for example, R ₁ to
In addition to the same alkyl group, substituted alkyl group, aryl group and halogen atom as the group which may be substituted by R ₅ , a sulfonamide group (for example, a sulfonamide group having an alkyl group having up to 4 carbon atoms substituted), carbamoyl A group (for example, an unsubstituted carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group, etc.) is preferred. Specific examples of the spectral sensitizing dye represented by formula (I) of the invention are shown below, but the invention is not limited thereto.

[0031]

[Chemical 3]

[0032]

[Chemical 4]

[0033]

[Chemical 5]

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

The above-mentioned merocyanine dyes are described, for example, in US Pat.
It can be obtained by the method described in No. 2493747 or No. 2656351 or a synthetic method similar thereto. Next, the hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0041]

[Chemical 12]

In the present invention, among these, the following general formula [H-a], [H-b], [H-c] or [H-] is used.
The compound represented by d] is preferable.

[0043]

[Chemical 13]

In the above general formula [Ha], R ₁₁ and R ₁₂
Hydrogen atom, substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, butyl group, dodecyl group,
2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (for example, phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-
Methylcyclohexyl group, pyridyl group, 4-propyl-2-
Pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group) and the like, and R ₁₃ is a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (for example, benzyl group, p-methylbenzyl group, methoxy group). Group, an ethoxy group, an ethyl group, a butyl group), R ₁₄ and R ₁₅ each represent a divalent aromatic group (eg, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents L. A divalent linking group (for example, —SO ₂ CH ₂ CH ₂ NH—, —S
O ₂ NH-, -OCH ₂ SO ₂ NH-, -O-, -CH = N-),
R ₁₆ represents —NR′R ″ or —OR ₁₇ , and R ′, R ″ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, dodecyl group), phenyl group ( For example, phenyl group, p-methylphenyl group, p-
Methoxyphenyl group), naphthyl group (eg α-naphthyl group, β-naphthyl group) or heterocyclic group (eg unsaturated heterocyclic group such as pyridine, thiophene, furan or saturated heterocyclic group such as tetrahydrofuran, sulfolane) And R ′ and R ″ may form a ring (for example, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

M and n each represent 0 or 1.
When R ₂₈ represents —OR ₂₉ , Y preferably represents a sulfur atom.

[0046]

[Chemical 14]

In the formula, R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group (eg methyl group, ethyl group, butyl group, 3-aryloxypropyl group), a substituted or unsubstituted phenyl group, a naphthyl group. , Cyclohexyl group, pyridyl group, pyrrolidyl group, substituted or unsubstituted alkoxy group (eg methoxy group, ethoxy group, butoxy group)
Alternatively, it represents a substituted or unsubstituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

In the present invention, R ₂₃ is preferably a hydrogen atom or an alkyl group.

R ₂₄ represents a divalent aromatic group (for example, a phenylene group or a naphthylene group), and Z represents a sulfur atom or an oxygen atom.

R ₂₅ is a substituted or unsubstituted alkyl group,
It represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group and an aryl group.

The hydrazine derivative can be easily synthesized by a known method. For example, JP-A-2-214850.
No. 2-47646, No. 2-12237 and the like.

Representative compounds represented by the above general formulas [Ha] and [Hb] are shown below.

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or represents a heterocyclic oxy group, R ₃₁ and R
₃₂ may form a ring with a nitrogen atom. When n = 2,
R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₃₁ and R
_At least one of ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. R ₃₃ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [A] or [B] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.), or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents.

R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl). Etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₃₁ and R ₃₂ together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

However, when n = 2, at least one of R ₃₁ and R ₃₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a hetero group. It represents a ring oxy group. Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₃₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Among these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercapto heterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Hc] and [Hd] are such compounds. Also includes.

More preferred compounds in the present invention are the compounds of the general formula [Hc] when n = 2, and the compounds of the general formula [Hd].

In the compound of n = 2 of the general formula [Hc], R ₃₁ and R ₃₂ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Typical compounds represented by the above general formulas [Hc] and [Hd] are shown below.
However, as a matter of course, the specific compounds of the general formulas [Hc] and [Hd] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0074]

[Chemical formula 23]

[0075]

[Chemical formula 24]

[0076]

[Chemical 25]

[0077]

[Chemical formula 26]

Specific compounds other than the above are disclosed in
2-841 No. 542 (4) to 546 (8) compound examples
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described in pages 2-841, 546 (8) to 550 (12). The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver, and more preferably 1 × 10 ^-5 mol to 1 per mol of silver.
× 10 ^-2 mol.

When [Hc] or [Hd] is contained as the hydrazine derivative, the nucleation promoting compound described in Japanese Patent Application No. 2-234203, page 68, line 1 to page 144, line 12 can be used. At least one kind is preferably contained in the silver halide emulsion layer and / or the non-photosensitive layer on the side of the silver halide emulsion layer on the support.

Typical examples of the nucleation accelerator are shown below.

[0082]

[Chemical 27]

[0083]

[Chemical 28]

Still another specific example is Japanese Patent Application No. 2-234203.
Nos. 69 to 72, compounds I-1 to I-26, 73 to 78, compounds II to II-29, 80 to 83
Compounds III-1 to III-25 described on page, Compounds IV-1 to IV-41 described on pages 84 to 90, Compounds VI-1 to VI described on pages 92 to 96 -27, compounds V-II-1 to V-II-30 described on pages 98 to 103, compounds V-III-1 to 113 described on pages 105 to 111, described on pages 113 to 121 Compounds VI-I-1 to VI-I-44, compounds VI-II-1 to VI-II-68 described on pages 123 to 135 and compounds described on pages 137 to 143 There are those other than the above-mentioned typical examples among VI-III-1 to VI-III-35.

The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) includes, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Although any of silver halide and silver chloride, which are commonly used in ordinary silver halide emulsions, can be used, preferably silver chlorobromide, silver bromide or 4 mol% or less of silver iodide is contained. It is silver iodobromide.

[(Standard deviation of particle size) / (average value of particle size)]
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable. Cd during and / or after grain formation
It is preferable to add salts, In salts, Rh salts, Tl salts, Zn salts, Pb salts, Ir salts (including silver salts). Particularly preferred is the addition of Ir salt (including complex salt). The addition amount is preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁸ mol per mol of silver.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, for the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents,
A development inhibitor, an ultraviolet absorber, an anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and the backing layer.

These additives are described in more detail in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979). It is summarized in the table below.

Additive Type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers pages 24 to 25, page 649, right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-staining agent Page 25 Right column Page 650 Left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Anti-stuck agent page 27 Same as above As the support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods after exposure, for example, a commonly used method.

The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, etc., and sulfites, carbonates, bisulfites of other alkali metal salts, and JP-A-56-56. -106244, amino compounds, bromides, iodides and the like can be included. The pH of the developer is preferably 10.2 to 12.0.

[0093]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide emulsion grains) A silver halide emulsion having a silver halide composition of 98 mol% silver bromide and 2 mol% silver iodide was used at 50 ° C., pAg 7.8 and pH 2.0. Was prepared under the following conditions. The silver ion and the haloid ion are supplied by the simultaneous mixing method,
At that time, the supply amount was increased in proportion to the surface area as the silver halide grains formed grew. Further, immediately before the completion of grain formation, 6 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver, and after completion of grain formation, partial halogen substitution was carried out using 0.3 mol of potassium iodide per mol of silver. After that, desalting is performed by a conventional method, and the following compounds [A], [B], [C]
An ossein gelatin solution containing the mixture of was added and redispersed.

The obtained emulsion had an average grain size of 0.2 μm and a coefficient of variation.
The emulsion consisted of 10% cubic grains. The compound represented by the formula (I) of the present invention or the comparative compound was added at 4.5 × 10 ⁻⁴ mol per mol of silver, and then sulfur was added for chemical sensitization.

[0096]

[Chemical 29]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer of the following formula (1) was coated so that the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ² , and the following formula (2) ) Is coated so that the amount of gelatin is 1.0 g / m ^2, and on the other undercoat layer on the opposite side, a backing layer is provided with a gelatin amount of 2.4 g / m 2 according to the following prescription (3). We paint so that it becomes ² .
On top of that, a protective layer of the following formula (4) is provided with a gelatin amount
A sample was obtained by coating so as to have a concentration of 1.0 g / m ² .

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: 5-nitroindazole 10 mg / m ² : 1-phenyl-5 -Mercaptotetrazole ² mg / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Hydrazine derivative (shown in Table 1) 3 × 10 ^-5 mol / m
² Surfactant: sodium dodecylbenzene sulfonate 0.1
g / m ²

[0099]

[Chemical 30]

Formulation (2) (Emulsion protective layer composition) Gelatin 0.9 g / m ² Matting agent: Silica having an average particle size of 3.5 μm 10 mg / m ²

[0101]

[Chemical 31]

Gelatin
2.4 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 0.1 mg / m ² S-1: 6.0 mg / m ² Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: Average particle size 3.0 to 5.0 μm polymethyl methacrylate 50 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² : H-1 35 mg / m ² Quality of the obtained sample according to the following test method Tests were conducted and samples were evaluated. The results are shown in Table 1.

(Black spot quality test method) Pattern exposure of halftone dots was performed with a plate making scanner SG747RU manufactured by Dainippon Screen Co., Ltd. This sample was subjected to development processing under the following conditions with an automatic developing machine for rapid processing in which a developing solution and a fixing solution having the following developing solution formulation and fixing solution formulation were introduced.

The halftone dots were observed with a magnifying glass of 100 times, and the one having no black spots in the halftone dots was given the highest rank "5", and ranked according to the degree of occurrence of black spots in the halftone dots. The ranks of “4”, “3”, “2”, and “1” are sequentially lowered and evaluated. Incidentally, in the ranks "1" and "2", black spots are large, which is a level that is not preferable in practical use.

The obtained sample was placed under the condition of 23 ° C. and 50% RH for 24 hours.
After storage for a period of time, it was hermetically sealed (storage I) and left at 55 ° C. for 3 days under high temperature storage conditions (storage II). The thermoprocessed sample was similarly exposed and developed and fixed.

(Evaluation of sensitivity, safelight property and residual color)
Each of the obtained sample films was exposed with a helium-neon laser, and the processing conditions were as follows.

The unexposed sample of the sample film was put on a 60 W tungsten lamp by a Konica safelight filter.
The fog density was measured by a conventional method when the sample was placed at a distance of 1 m under a green light through No. 5A and left for 30 minutes.

A fog density of 0.08 or more is a level which is regarded as a major drawback.

Table 2 shows the sensitivity of each sample and the measurement result of the fog density under each condition. The sensitivity is represented by the reciprocal of the exposure amount at fog density + 3.0 and the relative sensitivity with No. 101 sensitivity as 100.

Further, four sheets of the sample which had been processed without exposure were piled up and the residual color of the film was visually evaluated to give a five-level evaluation. "5" was colorless and "1" was a strong blue-purple color. It showed a residual color. The residual color of less than "3" for general platemaking is a major defect level.

<Processing Conditions> The processing conditions are as follows.

[Developer formulation] Sodium bisulfite 40g N-methyl-P-amonophenol sulfate 350mg Ethylenediaminetetraacetic acid disodium salt 1g Sodium chloride 5g Potassium bromide
1.2g trisodium phosphate
75 g 5-Methylbenztriazole 250 mg 2-Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Amine compound Am-1 0.5 ml Potassium hydroxide Amount to make the pH of the working solution 11.6 Add water at the time of use to 1 l Finished

[0113]

[Chemical 32]

[Fixing solution formulation] Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W / V) V aqueous solution) 15.7g Gluconic acid (50% W / W aqueous solution) 8.55g Aluminum sulphate (48% W / W aqueous solution) 13ml Glutaraldehyde 3g Sulfuric acid The pH of the working solution is 4.6. Add water when using to make 1l. It was

[Development Processing Conditions] Process Temperature Time Image 38 ° C. 20 seconds Fixing 38 ° C. 20 seconds Water washing Normal temperature 15 seconds Drying 40 ° C. 15 seconds The results are shown in Table 1.

[0116]

[Table 1]

[0117]

[Chemical 33]

From the results shown in Table 1, it can be seen that the sample of the present invention has little residual color, good safelight property, and few black spots.

Example 2 Example 1 was repeated except that a nucleation accelerator N-10 was added to the silver halide emulsion layer in an amount of 3 × 10 ^-5 mol / m ² and the following formulation was used as a developing solution. It was The results are shown in Table 2.

[Developer formulation] (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 ml 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to adjust the pH of the used solution to 10.5 Potassium bromide 4.5 g (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid dipotassium salt 25 mg Acetic acid ( 90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, it was dissolved in 500 ml of water to the above-mentioned composition A and composition B, and finished to 1 liter for use.

[0121]

[Table 2]

From the results shown in Table 2, as in Example 1, the sample of the present invention gave good results.

[0123]

EFFECTS OF THE INVENTION According to the present invention, halogenation having high sensitivity in the red wavelength region, little residual color after development, little black spots even when stored at high temperature, and good safelight property. It was possible to provide a silver photographic light-sensitive material.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A halogenation characterized by being spectrally sensitized with at least one spectral sensitizing dye selected from the following general formula [I], and containing a hydrazine derivative in the silver halide emulsion layer and / or its adjacent layer. Silver photographic light-sensitive material. [Chemical 1] [In the formula, Z represents an atomic group necessary for completing a thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, or naphthoselenazole ring.
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group. However, R ₁ , R ₂ , R ₃ , R ₄ and R
_At least two of ₅ represent groups having an organic group carrying a water-soluble group. ] 2. At least one of the water-soluble groups is an acid or base which can be ionized in an aqueous solution, and is a sensitizing dye having a water-soluble group having a pKa of 4 to 11. The silver halide photographic light-sensitive material according to claim 1. 3. At least one of the water-soluble groups is
3. The silver halide photographic light-sensitive material according to claim 2, which is a sensitizing dye having a water-soluble group having a pKa of 4 or less.